Polycarboxylic acid condensate of a terpene alcohol-formaldehyde product



Patented Aug. 28, 1945 POLYCARBOXYLIC ACID' CONDENSATE OF A TERPENEALCOHOL-FORMALDEHYDE PRODUCT Mortimer T. Harvey, EastOrange, N. Jassignor to Harvel Research Corporation, a corporation of New Jersey NoDrawing. Application April 29,1942, Serial No. 440,983

2 Claims.

The present invention relat 5Q: condensation products of polycarboxylicorgani acids with the products of condensation of formaldehyde withtertiary alcohols and to methods and steps of making and using saidproducts.

An object of the present invention is to make a material which can beused for surface coatings, for impregnations, for molded products andarticles and for use generally.

Another object of the present invention is to make a liquid condensationmaterial which can be further condensed to a solid state and which canbe used for general purposes.

Other objects and advantages of the present invention will appear forthe following descriptive and illustrative disclosure and from theappended claims forming part hereof.

Stated generally, the present invention com-. prises condensing atertiary alcohol with formaldehyde to obtain a liquid product, andcondensing said liquid product, with a polycarboxylic organic acid.

In the appended claims, where a polycarboxylic organic acid is stated,both said acid and its anhydride are meant, for example, maleic acid isintended to mean both maleic acid itself and maleic anhydride, andphthalic acid is meant to cover both phthalic acid and phthalicanhydride.

The condensation products of formaldehyde and tertiary alcohols, used inmaking the products of the present invention, are disclosed and claimedin my copending applications, Ser. Nos. 190,038 filed Feb. 11, 1938;202,361 filed April 15, 1938 and since abandoned; and 216,477 filed June29, 1938. Examples of tertiary alcohol suitable for use in the practiceof the present invention are pine oil, terpineol, tertiary butylalcohol, tertiary amyl alcohol, the tertiary hexyl alcohols, and others,including the tertiary alcohols disclosed in the above identifiedcopending applications to which reference is hereby made.

The above identified copending applications also disclose sulphuric acidand hydrochloric acid as suitable condensation catalysts for producingthe aldehyde-tertiary alcohol condensation products used as reagents inthe practice of the present invention.

The condensation products which may be used as reagents in the practiceof this invention are the organic liquids obtained by heat condensationof formaldehyde and a monomeric terpene alcohol in contact with waterand an acid catalyst, which organic liquid has a boiling point'cellulose nitrate.

The following examples will illustrate methods and steps of making theproducts of the present invention and the products themselves.

Ewample 1 A. Cne mole of steam distilled pine oil and three moles ofcommercial formalin, water solution of formaldehyde (about 37.5%) withabout one-half per cent (0.5%) of the total weight of the pineoil andthe. formalin of concentrated sulphuric acid in an equal volume ofwater, as condensing agent,

12 lbs. 8 ounces of steam distilled pine oil, about 20 lbs. 6 ounces of37.5% 01-120 solution, and about 47 c. c. conc. H2804 (C. P.) on 47 c.c. of water, are reacted as follows. The water solution of sulphuricacid is'added to the formaldehyde solution, after which the steamdistilled pine oil is added, and the mixture heated under a refluxcondenser. At the beginning and for several hours during the heating thepine oil floats on the formaldehyde solution, but after about six orseven hours a reaction takes place whereby an oily liquid reactionproduct is formed which goes to the bottom of the container with thewater present floating in it. The heating is then discontinued and thewhole is neutralized by the addition of about grams of NaOH dissolved in230 grams of water. The neutralized mate-rial is cooled and the bottom,oil layer is siphoned off. This material is hereinafter calledcondensation product 1A and is an organic liquid having a boiling pointabove 200 C. at 4 cm. of mercury and has a specific gravity of between1.09 to about 1.1 at 15 C.

B. About fifty (50) parts by weight of condensation product 1A andseventeen (17) parts by weight of maleic anhydride were heated under areflux condenser for about one hour; at C. The reflux condenser was thenremoved and the temperature raised to about 250 C. and held there forabout fifteen (15) minutes and then weight.

cooled. A condensation reaction took place whereby was produced aproduct, hereinafter called condensation product 18, which was thickerthan condensation product 1A and was of about the consistency of newhoney. This product can be thickened by continued heating throughvarious stages of thickness to a hard rosin like consistency when cool.

Condensation product 13 is suitable by itself and also with othermaterials for making surface coating, impregnations and for general use.For example, the condensation product 113, in amount resulting from themethod of 1B, fourteen and four-tenths (14.4) by weight of glycerol andforty-six and one-half (46.5) parts of water white rosin are added andthe whole heated up and held at about 250 C. for about fifteen (15)minutes (to form a hard bottom when cold). The mixture at this point waschilled back with one hundred and ten parts (110) of ester gum, and thetemperature heldat about 200 C. for about flve minutes. This product,hereinafter called, product 132, is soluble 'in linseed oil and issuitable for use whenever ester gums, rosin and resins generally areused for making surface coating, impregnations and for general use. Inthis latter example it is considered that one OH radicle water wasremoved, and to this distillate, which of the glycerol reacts with onemole of the resin and two OH radicles of the glycerol react with twocarboxyl groups of the maleic anhydride.

Example 2 B. About 120 parts by weight of product 1A, described above,and 49 parts of maleic anhydride are heated under a reflux condenser forabout two hours, after which about forty-six (46) parts of glycerol andabout one hundred and thirty (130) parts of rosin are added and thewhole heated under vacuum first for about one and one-half hours atabout 150 (1., then for about 1% hours at about 210 C., and finally forabout one-quarter hour at about 240 C. In a receiver connected in thevacuum system about 18 parts by weight of water and about 16 parts of alight volatile oil are caught. The condensation product of the reactionis a dry, hard and pale resin.

Example 3 A. Three moles of formaldehyde and one mole of tertiary butylalcohol, with 960 parts by weight 50 tionating column and the cut to 97C. taken ofl.

This cut was then re-distilled through the fractionating column until adistillate commenced to come over which dissolves cellulose acetate, thetemperature at this point being 87 C. This distillate, up to but notincluding the part at which 'it commenced to dissolve cellulose acetate,is

called product a, and was about forty parts by The residue from thisre-distillation separated into two layers in the flask, water insoluble(or only slightly soluble), organic .compounds in the upper layer andwater containing dissolved organic compounds in the lower layer.

The main residue, from the'flrst distillation, was then distilled atatmospheric pressure, without the fractionating column, imtil all of theacetate slowly.

contained water and water insoluble organic material, was added theresidue of the re-distillation described in the above paragraph and thenthe mixture was distilled through the fractionating column until no morewater insoluble material came over with the distillate which contained aconsiderable proportion of water, when the distillation wasdiscontinued. This distillate separated into two layers, a top layer ofwater insoluble organic material, here called product b, and a lowerlayer which is water containing some water soluble organic materials.The total yield of product -b was about one hundred parts by weight.

The water-free residue obtained upon the redistillation of the mainresidue, described in the next above paragraph, was distilled at reducedpressure at about forty millimeters of mercury up to a point where a,material which is water insoluble came over, the distillate being calledhere product 0, and the residue called product d. Said product 0 wasabout 285 parts by weight, is

water soluble and has a specific gravity of 1.08.

Said product d weighed about parts and contained some salts.

In this Example 3 the term water insoluble used to identify it frommaterial which is completely soluble in water, and it is noted here thatthe products here called water insoluble are slightly soluble in water.Also, it is noted that certain mixtures of the products which arecompletely soluble in water and the products which are only slightlysoluble in water form solutions which are soluble in water; for example,a mixture of product I) with product 0 is soluble in water and alsomakes a solution which is a fairly fast solvent for cellulose acetate.

Product a is low-boiling (up to about 87 C.), is water soluble anddissolves cellulose nitrate.

Product I; boils at an intermediate temperature (about 90 C. to aboutC.), is water insoluble and dissolves cellulose acetate quickly.

Product 0 is high boiling (about C. to about 250 0.), is water solubleand dissolves cellulose Example 3 B. About seventy parts by weight ofsaid product c (of 3A above) and forty-nine parts of maleic anhydrideare heated under a reflux condenser for about two hours in the manner ofExample 23, described above and the addition of glycerol and rosincarried on in the manner and in the. proportions described in saidExample 23. The condensation product is a dry, hard and pale resinhaving a high melting point.

The reaction product of product 0 and maleic anhydride can be used atvarious stages of consistency from a slightly viscous liquid to a hardrosin-like consistency in a manner and for purposes similar to thosedescribed for product 13 above.

Example 4 A. About three moles of benzaldehyde and one mole of tertiarybutyl alcohol and about 1% of their total weight in concentratedsulphuric acid are heated at about 300 F. for about six hours under areflux condenser after which those materialsare removed by distillationwhich have boiling points up to 205 and about sixteen parts of theresidue are heated with seven parts 01 maleic anhydride for aboutone-half hour at asaavoi The present application is acontinuation-inpart of my application Ser. No. 238,813 filed November4,-1938.

Having thus described my invention, what I claim and desire to protectby letters Patent is: 1. The product of condensation under acidcondition of maleic anhydride with an organic liquid which is obtainedby heat condensation of formaldehyde and a monomeric terpene alcohol incontact with water and an acid cataLvst, which organic liquid has aboiling point above 200 C. at '4 cm. of mercury and which has a'specific gravity of about 1.09 to about 1.1 at 15 C.

2. The resinifiable condensation product of material selected from thegroup consisting of nucleic acid and phthalic acid withan organic liquidwhich is obtained by the heat condensation of formaldehyde and amonomeric terpene alcohol in contact with water and an acid catalyst,which organic liquid has a boiling point above 200 C. at 4 cm. ofmercury and which has a specific gravity of about 1.09 to about 1.1 at.15 C.

